Dynamic Properties of Misdirected Ligand Complexes

错误定向配体复合物的动态性质

• 批准号: 9612869
• 负责人: Michael Ashby
• 金额: $ 31.1万
• 依托单位: University of Oklahoma Norman Campus
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-01-01 至 2000-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9612869&HistoricalAwards=false
• 关键词: Dynamic; Properties; Misdirected; Ligand; Complexes

Dr. Michael T. Ashby, Department of Chemistry, University of Oklahoma, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for a study of metal complexes containing ligands that are geometrically constrained so that they cannot donate pi electrons to the metal. Because their orientation precludes them from utilizing their maximum number of electrons in bonding with the metal, these ligands are termed `misdirected.` The project will address the fundamental questions of how can a ligand be `misdirected,` but still be firmly attached to a metal; the effects of `misdirected` ligands on the ground-state and transient properties of transition metal complexes; and the possibility that ligand `misdirection` and `redirection` can have practical application. To address these questions a series of complexes will be synthesized utilizing ligands that can be forced to shuttle between a conformation that allows pi interaction with the metal and one that is `misdirected.` The dynamic conformational properties of these complexes will be studied and the influence of ligand `misdirection` on the chemical properties of the complexes will be assessed. Many chemical reactions carried out in the laboratory, in industry, and by biological systems involve the participation of metal ions. Much of the unique reactivity of the metals is a reflection of variations, during the course of reactions, in the number of electrons surrounding the metal. This project will probe fundamental questions of how complexes can be designed so that groups attached to metal ions can be forced to provide variable numbers of electrons. Systems will be studied to determine both how to obtain such compounds and how controlled alterations in the metal electron counts can change chemical reactivity. This will set the ground work both to understand existing processes and to rationally design new ones.

Michael T.俄克拉荷马州大学化学系的阿什比是 由无机，生物无机和有机物计划支持， 化学部，研究含配体的金属络合物 它们在几何上受到限制， 电子到金属。因为他们的取向使他们无法 利用它们与金属键合的最大电子数， 这些配体被称为“错误定向的”。该项目将解决 一个配体如何被“误导”，但仍然是一个基本的问题， 牢固地附着在金属上;“错误”配体对金属的影响 过渡金属络合物的基态和瞬态性质;以及 配体“错误导向”和“重定向”可能具有 实际应用为了解决这些问题， 将利用配体合成， 在允许π与金属相互作用的构象和允许π与金属相互作用的构象之间 这是“误导”。这些分子的动态构象性质 配合物将被研究和影响的配体“误导”， 将评估络合物的化学性质。 许多化学反应在实验室、工业和 涉及到金属离子的参与。大部分 金属的独特反应性是变化的反映， 反应的过程，在周围的电子数 金属.这个项目将探讨复合体如何 被设计成使得与金属离子连接的基团可以被强制 提供可变数量的电子。将研究系统， 确定如何获得这些化合物以及如何控制 金属电子计数的改变可以改变化学反应性。 这将为理解现有流程和 合理设计新的。